Sulfonate ester-containing two-equivalent yellow-forming couplers



United States Patent Int. Cl. C07c 143/68 US. Cl. 260-456 4 Claims ABSTRACT OF THE DISCLOSURE Alpha-sulfonyloxy substituted 2-equivalent yellow dyeforming couplers are used to advantage for forming yellow dye images in color photography, particularly because these couplers are characterized by not producing color fog and having very good coupling reactivity.

This is a division of application Ser. No. 444,822, filed Apr. 1, 1965, now Pat. No. 3,415,652 issued Dec. 10, 1968.

This invention relates to color photography and more particularly to novel dye-forming coupler compounds for use in image forming systems and processes utilizing such compounds for the formation of images. In particular, my invention relates to two-equivalent coupler compounds for forming yellow dye images in color photography.

The formation of colored photographic images by coupling the oxidation product of an aromatic amino developing agent with color-forming compounds is well known. Presently, the subtractive color process is most frequently used, and the image dyes are of the primary colors cyan, magenta and yellow for the red, green and blue records repsectively. The couplers which form the cyan dyes are usually phenols or naphthols; those forming the magenta dyes are generally pyrazolones or cyanoacetyl compounds; and those forming the yellow dyes are open-chain compounds containing a methylene group having two carbonyl groups attached to it.

Most of the above mentioned couplers which have !been used in the previously described color processes are four-equivalent couplers, that is, they require 4 mols of silver halide for the formation of 1 mol of dye. However, certain of the prior art couplers which are twoequivalent couplers, i.e., requiring only 2 mols of silver halide for the formation of 1 mol of dye, for example the couplers described in French Pat. 991,453, British Pat. 805,505, etc. New two-equivalent couplers are desired that have improved characteristics for use in color photography.

It is an object of my invention to provide novel improved couplers which are capable of forming yellow dye with the oxidation product of an aromatic amino color developing agent. It is a further object of my invention to provide new and improved couplers capable of forming yellow dye with the oxidation product of an aromatic amino developing agent and which couplers require less silver halide development to produce a given amount of dye than do the analogous prior art fourequivalent couplers. It is a further object of my invention to provide new and improved two-equivalent low-. fogging yellow-forming couplers having good reactivity so that processing can be accomplished in a reasonable time and without prolonging development or without requirement for excessively high pH or high temperature processing conditions. Another object is to provide new Patented Nov. 24, 1970 "ice two-equivalent couplers which have good reactivity even when incorporated in silver halide emulsion layers without any high boiling coupler solvents. Another object is to provide new couplers which are valuable for use in any of the image forming systems (silver or nonsilver) where couplers are used to advantage, for example the coupler can be used to advantage in image forming layers either alone or together with image forming compounds other than silver halide, such as, for example zinc oxide, cadmium sulfide, cadmium selenide, zinc sulfide, nickel sulfide, etc., either with or without a binder.

These and other objects which will appear from the following description of my invention are accomplished by the use of my a-sulfonyloxy substituted two-equivalent couplers.

My compounds retain the advantage of the prior art two-equivalent couplers while, at the same time avoid the disadvantage of color fog. Further, my couplers exhibit 'a high reactivity, unlike many of the previously described two-equivalent couplers. The sulfonyloxy group appears to be more readily eliminated from the coupler during the coupling reaction (i.e., with oxidized color developer) than does any one of a number of the prior art coupling-off groups. Consequently, my couplers exhibit a higher reactivity in the color-forming or coupling reaction.

My new couplers contain at least one open chain nucleus containing an active methylene group separating and joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, said active methylene group having only one hydrogen atom substituted by a R SO O- group wherein R is a carbon-containing radical. The said acyl and said amide radicals can be any of the acyl and amide radicals found in known coupler compounds since my couplers are derived to advantage from any of the known four-equivalent couplers. For example, the acyl radical can contain an organic radical that is open chain, isocyclic, bicyclic, heterocyclic, etc., in which each of these radicals can be saturated, unsaturated, substituted or unsubstituted. The amide radical can contain an amino group or any of the substituted amino groups found in couplers.

My new class of couplers includes those represented by the following formula:

wherein n represents 1 or 2, H represents an organic radical, e.g., open chain isocyclic, bicyclic, heterocyclic, etc., in which the radicals can be saturated, unsaturated, substituted, or unsubstituted, for example, an alkyl group, especially those having from 1 to 22 carbon atoms, e.g., methyl, 3-pentadecylphenoxymethyl, ethyl, phenylethyl, n-propyl, isopropyl, a(2,4-di-t-amylphenoxy)-propyl, 6- sulfobutyl, sec-butyl tert-butyl, docosyl, chloromethyl, trifluoromethyl, Z-hydroxyethyl, fl-carboxyethyl, 2-(2,4,6- trichlorophenyl)ethyl, Z-aminoethyl, u,a-dimethylbutyl, u methoxy on methyloctyl, 0c propyl a octyldocosyl, a, a dibutyl docosyl, 06,0: di decylundecyl, 0:,04 di t butyldodecyl, a, a di sec butylpentadecyl, etc., a terpenyl group, especially groups, such as 7,7- dimethylnorbornyl, 2 alkyl 7,7 dimethylnorbornyl radicals in which the alkyl group has from 1 to 18 carbon atoms, such as methyl, butyl, octadecyl, etc., for example, 2 methyl 7,7 dimethylnorbornyl, 2 octadecyl 7,7-

(21 a- [4-( 8-acetamido-3,6-disulfo- 1 -hydroxy-2- naphthylazo) phenylsulfonyloxy] -u-pivalyl-3- ['y- 2,4- di-t-amylphenoxy)butyramido)acetanilide The couplers of my invention are nondifiusible and are used to advantage in photographic emulsion layers. Couplers such as Nos. 11 and 12 illustrate those that are incorporated as Fischer-type couplers. The other couplers such as Nos. 1-6 and 13-20 are incorporated in emulsion layers by methods such as those described by US. Pat. 2,304,939, issued Dec. 15, 1942, US. Pat. 2,322,027, issued June 15, 1943, etc., in which high boiling organic solvents are used to dissolve the coupler, and by methods described in US. Pat. 2,801,170, and Pat. 2,801,171, both issued July 30, 1957, US. Pat. 2,949,360, issued Aug. 16, 1960, in which low boiling or water soluble solvents are used with or in place of the high boiling solvent. Not only can emulsion layers containing my couplers be made thinner becausethey require only one-half the silver halide required by conventional couplers (i.e., fourequivalent couplers), but some of my couplers are sufficiently reactive so that they do not require any high boiling coupler solvent that is usually required by couplers. The thin image-forming layers are very desirable because they cause less light scattering and produce sharper images. Coupler No. 8 forms a diffusible dye upon color development and can be used to advantage either in image transfer elements or in emulsion layers as a non-imageforming competing coupler together with an image-forming competing coupler. Coupler No. 7 has a sulfarnyl group on a non-coupling position which ionizes and forms a ditfusible dye upon color development at a pH above 11 and a nondiffusible dye at a pH below 11. Coupler .No. 21 contains a preformed dye attached to the coupler on the phenylsulfonyloxy group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film. This coupler can be used as a magenta-colored coupler for the purpose of correcting for the unwanted green absorption of yellow image dye, i.e., that formed from the coupler itself as well as that formed from other yellow couplers. Generally, such a coupler as this would be used in combination with another image-forming yellow coupler in the same layer. I

Any of the well-known primary aromatic amino colorforming silver halide developing agents such as the phenylene-diamines, e.g., diethyl-p-phenylenediamine hydrochloride, mono-methyl p phenylenediamine hydrochloride, dimethyl-p-phenylene diarnine hydrochloride, 2-

amino-S-diethylaminotoluene hydrochloride, 2-amino-5- (N-ethyl-N-lauryl)toluene, Nethylfi-methanesulfonamidoethyl-3-methyl 4 aminoaniline sulfate, N-ethyl-fimethanesu1fonarnidoethy1-4-aminoaniline, 4-N-ethyl-N-B- hydroxyethylaminoaniline, etc., the p-aminophenols and their substitution products Where theamino group is unsubstituted may be used to develop photographic coatings containing my couplers. Variousother materials may be included in the developer solutions depending upon the particular requirements,for example, an alkali metal sulterial.

Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in US. Pat. 2,286,215, a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26%,

as described in US. Pat. 2,327,808, a water-soluble ethanolamine cellulose acetate as described in US. Pat. 2,322,085; a polyacrylamide having a combined acrylamide content of 30-60% and a specific viscosity of 0.25- 1.5 or an imidized polyacrylamide of like acrylamide content and viscosity as described in US. Pat. 2,541,474, zein as described in US Pat. 2,563,791, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in US. Pat. 2,768,154, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in U.S. Pat. 2,808,331, or a polymeric material which results from polymerizing a protein or a saturated acrylated protein with a monomer having a vinyl group as described in U.S. Pat. 2,852,382.

The emulsions used in the photographic element of my invention can contain any of the addenda used in photographic materials, for example they can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added. The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition. The emulsions can also be chemically sensitized with gold salts, or stabilized with gold salts. The emulsions can also be optically sensitized with dyes such as cyanine and merocyanine dyes. The emulsions may also contain speed-increasing compounds of the quaternary ammonium type or of the polyethylene glycol type.

The above-described emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass and others.

Usually my emulsions are coated on photographic supports in the form of multilayer color photographic elernents wherein at least three differently sensitized emul sion layers are coated over one another on the support. Usually the support is coated in succession with a redsensitive layer, a green-sensitive layer and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these lightsensitive layers are arranged on the same side of the support.

Elements made for image transfer processing may use a separate reception sheet which is contacted with the light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet. The reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in US. Pat. 2,882,156, granted Apr. 14, 1959.

Single layer camera speed gelatin silver bromoiodide emulsions containing yellow-forming coupler and coupler solvent di-n-butyl phthalate were made for my couplers Nos. 3, 4 and 5 respectively. The coatings contained 10 parts of gelatin, parts of silver halide, 2 parts of coupler and 1 part of coupler solvent by weight.

Strips of the above Coatings were given -second exposure on a 1B intensity scale sensitometer and processed through the following process:

Time: Process steps 30" Water dip. Development. 5' Stop bath. 5' Ferricyanide bleach. 5 Wash. 5' Fixing bath. 10' Wash. 30" Photo-Flo (wetting agent solution).

The following developer solutions were used:

Developer 1 Sodium sulfite (anhydrous)2 g. 2-amino-5-diethylaminotoluene HCl2 g. Sodium carbonate monohydrate g. Potassium bromide2 g. Water to1 liter. pH 10.86.

Developer 2 The resulting yellow dye images were observed with a spectrophotometer to determine the A values and examined with a densitometer to determine the D values. The photo data are given for the above mentioned processed strips in Table I.

TABLE I Developer N o Dmnx Mm Coupler N o.:

EXAMPLE 2.

Single layer coatings similar to those described in Example 1 were prepared using Couplers 3, 4 and 5, respectively, except that in making these coatings no high boiling coupler solvent was used. In place of the di-nbutyl phthalate coupler solvent used in the coatings of Example 1, the couplers were dispersed using ethyl acetate as the only solvent. Typically, after such a dispersion is made it is chilled and the ethyl acetate solvent is removed by washing the chilled gelatin dispersion with cold water. This technique of dispersing couplers has been previously disclosed in the literature reference above. These coatings were processed in the same manner as those of Example 1. Photo data similar to that obtained in Example 1 were also obtained on these processed strips. This data is given in Table 11 below.

A comparison of the D values given for these dye images with those for the same couplers in the coatings of Example 1 shows clearly that the reactivity of the coupler remains essentially unchanged when coated with no coupler solvent.

EXAMPLE 3 Single layer coatings similar in structure to those given in Example 1 above were made containing Compound 1. The coating containing this coupler was exposed and processed similar to the process given in Example 1 above using Developer 1 of Example 1. The D of the image dye in the coating containing my coupler No. l was 3.14.

EXAMPLE 4 Single layer coatings similar in structure to those given in Example 1 above are preferred using compounds Nos. 7 and 8, respectively. Exposed strips of these coatings are processed by developing them for five minutes at 75 F. in contact with a mordant containing receiving sheet which had been presoaked in the following developer solution.

G. Sodium carbonate monohydrate 22 Ascorbic acid 0.24 Potassium bromide 0.8 Sodium sulfite (anhydrous) 2.0 4-amino-N-ethyl-N-B-hydroxyethyl-aniline sulfate 11.0 Water to make 1.0 liter. pH adjusted to 12.5 using 20% sodium hydroxide solution.

After the development period, the films are removed from the mordant receiving sheets in which sheets are contained the transferred and mordanted yellow dye images respectively.

Similarly, other couplers of my invention are used to advantage in color photography as illustrated previously with representative couplers. Further, the couplers of my invention are valuable as yellow image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film. Such other couplers are, for example, magenta-forming pyrazolones, cyanoacetyl coumarones, indazolones, etc., and cyan couplers such as naphthols and phenols.

In general, my couplers are prepared from the parent coupler having the formula:

Br Br wherein R, R and R are as described previously, by reacting the parent coupler with the silver salt of a sulfonic acid, said salt having the formula [AgOSO R in which R and n are as defined previously. The above mentioned a-bromo couplers can be prepared by methods similar to those in, for example, McCrossen et al. US. Pat. 2,728,658, issued Dec. 27, 1955, in which patent is described the preparation of a-ChlOlO yellow couplers.

The following preparation of coupler No. 4 will illustrate the syntheses of my yellow forming couplers.

A mixture of 26 g. of a-bromo-a-pivalyl-4-(N-methyl- N-octadecylsulfamyl)acetanilide and 9 g. of methyl sulfonic acid silver salt in 400 ml. of acetonitrile was refluxed for 24 hours, after which time the silver bromide which precipitated was collected. The filtrate was concentrated in vacuo and the residue was dissolved in 500 ml. of ethyl acetate, which solution was filtered to remove a small amount of insoluble material. This filtrate was washed with water, twice with 250 ml. portions of 1% sodium bromide solution, and then dried over sodium sulfate. The dried solution was separated from the sodium sulfate and concentrated in vacuo. The solid residue was recrystallized twice from 300 ml. of acetonitrile, yielding 23 g. of product, M.P. 9496 C.

Couplers 1-8 and 11-19 are prepared by similar reactions using the intermediates given in Table III below.

The invention has been described in detail with particlar reference to preferred embodiments thereof but it will butyrainid]benzoy1 l-2-methoxyaeetanilide. a-Brorno-a-pivalyl-4-sulfamylacetanilide.

a-Brom0a-pivalyl-3,5-dicarboxyacetanilide a-Bromo-a-(Z-methoxybenzoyl)-4-[a-(2,4'di-t amylphenoxy)-5-(3-suliobenzamido)benzamido} acetanilide sodium salt. 12 u-Bromo-a-l3-[a-(2,4-di-t-amylphenoxy)butyramid0]benzoyll-Z-methoxyacetanilide.

13 Same as No. 12 above 14 a-Bromo-a-pivalyl-N,N-bis(carbethoxymethyl)- acetanilide.

15 a-Benzoy1-abromo-N-(4,5-dicarbethoxy-2- thiazolyDacetanilide.

16 a-Bromo-wfuroyM-[y-(3-pentadeeylphenoxy)- butyramido1acetanilide.

17 a-Bromo-w(7,7-dimethylnorbornyl-l-carbonyl)-3- palmitamido-acetanilide.

18 2 mols of a-Benzoyl-a-bromo-4'[a-(2,4-d1-t-amylphenoxy)acetamido1acetanilide.

19 a-Bromo-a-pivalyl-3-i'y-(2,4-di-t-amylphenoxy) butyramido1acetanilide.

4-octadecyloxybenzene sulfonic acid.

3-nitrobenzene sulfonic acid. Propyl-l sulfonic acid.

a-Garboxybutyl-l-sulfonie acid.

8-Oarboxymethoxybutyl-l-sulfonic acid.

Oetadecyl1-sulfonic acid.

Docosyl-l-sulfonie acid.

'y-flydroxypropyl-l-sulfonic acid.

8-ethoxyoctyl-1-sulfonic acid.

Ethyl-1,2-disulfonic acid disilver salt.

4-nitrobenzene sulfonic acid.

Compound No. 9 is prepared by the catalytic (i.e., using palladium on charcoal as the catalyst) reduction of Compound No. 8. Compound No. 10 is prepared by acylating Compound No. 9 using a-(3-pentadecylphenoxy) acetyl chloride in acetic acid containing sodium acetate as the condensing agent. Compound No. 20 is prepared by the catalytic (i.e., using palladium on charcoal as the catalyst) reduction of Compound No. 19. Compound No. 21 is prepared by the diazotization of Compound No. 20 and the subsequent coupling of the diazo salt with acetyl H-acid disodium salt.

The two-equivalent image-forming couplers of my invention are distinguished from other two-equivalent couplers by having a sulfonyloxy group substituted on the coupling position of the coupler molecule. My couplers are characterized by not producing color fog, a problem with certain prior art two-equivalent couplers, and by having very good coupling reactivity. These couplers are dispersed readily in emulsion layers as a coupler solvent solution having a wide range of coupler to solvent ratios.

My couplers are not only valuable for the reasons cited, but because photographic emulsion layers color developed with them require only one-half the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondifiusing couplers which have high coupling reactivity when dispersed in photographic emulsion layers without any high boiling solvent. These couplers are coated to advantage in particularly thin layers that produce good sharp images. The couplers of my invention may be used in emulsion layers either alone or admixed with other couplers, either four- 1or two-equivalent couplers, competing couplers, and the be understood that variations and modifications can be elfected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A two-equivalent yellow dye-forming coupler selected from the group consisting of u-methylsulfonyloxy-apivalyl-2-chloro-4-(N-methyl-N octadecylsulfamyl)acetanilide; a-methylsulfonyloxy-m-pivalyl-4-( N methyl N- octadecylsulfamyl)acetanilide and OL-methYISUIfOIIYIOXY-OL- pivalyl-2,5-dichloro4-(N-methyl-N octadecylsulfamyl) acetanilide.

2. The two-equivalent yellow dye-forming coupler ozmethylsulfonyloxy-a-pivalyl-2-chloro-4-(N methyl N- octadecylsulfamyl) acetanilide.

3. The two-equivalent yellow dye-forming coupler etmethylsulfonyloxy-a-pivalyl-4-(N-methyl N octadecylsulfamyl)acetanilide.

4. The two-equivalent yellow dye-forming coupler amethylsulfonyloxy-a-pivalyl-2,5-dichloro-4-(N-methyl N- octadecylsulfamyl) acetanilide.

References Cited UNITED STATES PATENTS 2,271,238 1/1942 Vittum 9656.6

LEON ZITVER, Primary Examiner L. DE CRESCENT E, Assistant Examiner US. Cl. X.R. 

